Dyestuffs of the naphthophenosafranine series



Patented F b. 18,1941

UNITED STATES PATENT OFFICE DYESTUFFS OF THE NAPHTHOPHENO- SAFRANINE SERIES 'Carl Hfifchen and Eugen Huber, Leverkusen I. G.-Werk, Germany, assignors to General Aniline & Film. Corporation,

Delaware a corporation of 18 Claims.

The present invention relates to new dyestuffs of the naphthophenosafranine series, to methods of preparing these dyestuffs, to the application of the said dyestuffs in the chromium printing process, and to'dyed fibers.

Up to the present time chrome dyestuffs of the naphthophenosafranine series have been comparatively unknown. In German Patent No. 97,365 (Example 3) a dyestuff is mentioned which is obtained by an oxidising condensation of p-aminosalicylic acid with neutral blue. The dyestuff is said to be difliculty soluble and. is said to dye wool reddish-violet, chromed wool dark blue.

In German Patent No. 97,396 (Example 4) a dyestuff is described which is obtained by an oxidising condensation of aminosalicylic acidwith the isorosinduline sulfonic acid obtained from 131M-p-tolylnaphthylamino sulfonic acid and nitrosodimethylaniline. .According to -this specification the dyestuff dyes wool in an acid bath violet, chromed wool blue shades.

Further in German specification No. 183,117 a dyestuff is described which is obtained by treating phenylisorosinduline chloride with oleum and by an oxidising condensation of p-aminosalicylic acid with the disulfonic acid obtained. The dyestuff contains 2 sulfonic acid groups which, according to present knowledge, are present in the phenyl nucleus attached to the position 3. The

, oxidising condensation as described in this patent takes place only with difllculty. According to this specification the dyestuff' dyes wool in an acid bath bluish violet shades.

In German Patent No. 87,671 a dyestuff from ditolyl-cups-naphthylenediamine-era-sulfonic acid and benzene'azosallcylic acid is described. According to this specification the dyestuff obtained dyes chromed wool bluish-red. On sulfonating the dyestuff a more easily soluble product is ob tained which is said to yield on wool red and on chromed wool beautiful bluish-red shades.

So far as the field of the chrome dyestuffs is concerned no practical results could be attained with the above processes. Regarding the possibility of using dyestuffs ofthe above mentioned character for the chromium printing process nothing was known hitherto.

According to the present invention dyestuffs of the naphthophenosafranine series can be employed with success for the chromium printing process. All those dyestuffs of the naphthophenosafranine series come into question which contain at least one hydroxy-carboxylic acid grouping and which further possess due to the presence of solubilizing groups, a solubility suificient for use in the chromium printing process' The present invention thus concerns using dyestuffs of this kind for the chromium printing process.

The term hydroxycarboxylic acid grouping comprises any groupings of a hydroxy and a carboxylic acid group, which are capable of forming chromium compounds. Preferably salicylic acid groupings and o-hydroxynaphthoic acid groupings and the substitution products thereof are concerned.

When used in the chromium printing process the dyestuffs show a good fixability on the ma-,

terials in question, a good fastness to washing, a goodresistance to discharging agents and clear shades of the prints. 1

Especially distinguished by an excellent resistance to discharging agents are those dyestuffs which are substituted in the nucleus I by halogen (cf. the following formula).

As printing processes suitable for the present invention may be mentioned, for instance: machine printing, film printing, hand printing, spray printing, relief printing. The printing process wth the specified dyestuffs can be employed especially on cotton, regenerated cellulose, cellulose esters, linen, wool, silk and mixed fabrics of these textile fibres.

The present invention further relates to new dyestuffs of the naphthophenosafranine series which can be used with good result also for other purposesthan for the chromium printin Plocess. The dyestuffs which here come into question are those of the following general formula:

in which one hydroxycarboxylic acid grouping must be present in one of the nuclei I, III or IV or in one of the substituents R1, R2 or R3, and further hydroxycarboxylic acid groupings can be present in any position of the dyestuif, and

wherein at least one sulfonic acid group must beisorosinduline-G-sulfonic acids, which either may 1 contain already a suitable hydroxy carboxylic acid grouping in the nuclei 1 orm, and react the same with any aromatic amine, diamine or their sulfonic acids, or the 6-sulfonic acid group may be replaced by an aromatic amino-hydroxycarboxylic acid notwithstanding the fact whether or not the nuclei I or III contain already a hydroxy-carboxylic acid grouping. The hydroxy-carboxylic acid groupings introduced by this replacement reaction may stand not only directly in the nucleus IV but also in the substituent R3 and here either as amino-hydroxycarboxylic acids or as amide'ot a hydroxy-carboxylic acid. In case the number of sulionic acid groups introduced by the synthesis does not warrant a sufllcient solubility of the dyestuff, furtreating the dyestufl with sulfonating agents.

The new dyestuffs are dark crystalline watersoluble powders which dissolve in concentrated sulfuric acid with green coloration,

Dyestuffs of the above formulaalsoyield good Enron: 1

1/20 mol of dianilido-p-acid and U20 mol of '-sulfo-4-hydroxy-3'-carboxy- Q-aminodiphenylamine-2-sulfonic acid are dissolved with 200 cos. of water and the necessary quantity of sodium carbonate to a weakly alkaline solution, and, after the addition of 200 cos. of alcohol and 85 cos. of an ammoniacal copper solution are condensed by oxidation with air.

BOaH

' Theseparated dyestuif dissolves in water with a reddish blue and in sulfuric acid with argreen coloration. V I

Chromium. Mint! 20 g. of the dyestuff are dissolved in 280 g. of water or in a mixture of water and asolvent,

ther sulfonic' acid groups may be introduced by material is steamed for' about one hour and then washed. In this manner vivid reddish blue shades are obtained. The dyestufl. also fixes well on naphtholized materials; it exhibits good fastness to washing and is very resistant to discharging agents.

' EXAMPLE 2 Similar in manufacture and dyeing qualities is the dyestufl which is obtained by an oxidizing condensation of dianilido-e-acid with 5-sulfo-3'-carboxy-2'- hydroxy 4 amino diphenylamine-2-sulfonic acid.

It yields, when printed with chromium mordant,

blue shades of good fastness to washing and is of a good resistance to discharging agents.

ExmLa 3 By heating of 3-diethylisorosinduline-L6-disulionic acid with 5-sulfo-3-amino-2-hydroxybenzoic acid in the presence of sodium acetate in an aqueous or dilute alcoholic solution, a dyestuif is obtained which dissolves in water with a blue, in sulfuric acid with a green coloration.

SOaH

HOaS

When printed with chromium mordant the dyeness properties are obtained.

Exm m4 By reacting 11-methyl-3-diethylisoroslnduline- 1.8-disulfonic acid with 5'-sulfo-4'-hydroxy-3'- carboxy-4-amino-diphenylamine-2-siflfonic acid at water bath temperature in the presence of sodium acetate in an aqueous or dilute alcoholic solution a dyestuff is obtained which dissolves in water with a clear blue coloration, in concentrated sulfuric acid with a green coloration. It dyes wool clear greenish-blue shades of good fastness' to light and washing, chromed wool somewhat less clear, but likewise of good f'astness properties.

SOzH

When printed with chromium mordant it yields clear blue shades of good fastness to washing and good resistance to discharging agents.

EXAMPLE 5 From 3-diethylisorosinduiine-1.6.12-trisulfonic acid and 2' hydroxy 3' --carboxy 4 aminodiphenylamine-Z-sulfonic acid, a dyestufl is obtained which dissolves in. water with a greenishblue, in concentrated sulfuric acid with a green coloration.

SOaH

SOsH

It dyes wool greenish-blue shades of good fastness properties.

When printed with chromium mordant on cotton, it yields a full blue of good fastness to washing and good resistance to discharging agents and it can also be fixed well on naphtholized material.

EXAMPLE 6 By heating of 11.13 dichloro 3 diethylisorosindu1ine-1.6-disulfonic acid with ,5-sulfo-3- amino-2-hydroxybenzoic acid in the presence of sodium acetate a dyestuii is formed of the constitution:

m SOBH Y Hols H 01 no 1 01 which dissolves in water with a clear greenishblue, in concentrated sulfuric acid with agreen coloration.

. When printed with chromium mordant on cotton the dyestufl yields clear greenish-blue shades of very good resistance to discharging agents and very good fastness to washing.

Exmru '7 If in the foregoing example instead of 5-sulfo- 3 amino 2 hydroxyhenzoic acid 5' suito- 4 hydroxy 3' carboxy 4 aminodiphenylamine-2-sulfonic acid is used a dyestuii' of the same good properties is obtained. The dyestuif corresponds in its free state to. the following OaH 1 EXAMPLE 8 By heating of 11-methyL-13-hydroxy-l4-carboxy-3-diethyl-isorosinduline-1.6-disulfonic acid with 5-sulfo-3-amino-2-hydroxybenmic acid in the presence of sodium acetate in an aqueous or a dilute alcoholic solution a dyestufl is obtained which dissolves in water with a blue, in sulfuric acid with a green coloration.

SOaH

H038 I QN N mom), 1100 n Printed with chromium mordant on cotton it yields clear blue shades of good fastness to washing and good resistance to discharging agents.

EXAMPLE 9 By reacting 8-carboxy-9-hydroxy-3-diethy isorosinduiine-LG-disuifonio acid with 5-sulf0-3- amino-Z-hydroxybenzoic acid in the presence of sodium acetate at water bath temperature, a dyestuf! is formed which dissolves in water with a violet, in concentrated sulfuric acid with a dull bluish-green coloration.

when printed with chromium mordant on cotton it yields a full violet of a good fastness to washing and good resistance to discharging agents.

; greenish-blue shades ofgood iastness pr p rties. When'printed with chromium mordant on Exmts 10 The dyestuif of the formula:

N CH: H O1N N N N(C:HI):

coon

H v is obtained by heating the 12-carboxy-13-hydroxy-3 diethyl isorosinduline-Ld-disulfonic acid with 5-amino 2 ethyl-toluidine and sulfonating the dyestuil' thus obtaind with five times the quantity of 20% oleum at about 70 C. The dyestufi dyes wool from an acid bath in cotton, reddish-blue shades likewise of good fastness properties are obtained.

Emu: 11

By heating iLlli-dimethyl-3-diethyl-isorosinduline-B-monostflfonic acid with B-sulfo-S- amino-2-hydronbenzoic acid a diflicultly soluble dyestufl' is obtained which issulfonated by several hours stirring with live times the quantity of 30% oleum.

Q4: Imam), N

HO O H H10 CHI when printed with chromium mordant on cotton a clear greenish blue, which also flxeswell on naphtholized. material, of good fastness to washing and good resistance to disc agentsisobtained.

Exams: 12 1 By reacting 11.13-dichloro-3-sulfoethylbutylisoroslnduline-fi-sulfonic acid with 5-su1fo-3- amino-2-hydroxybenroic acid at water bath temperature in the presence of sodium acetate a dyestuif of the following formula is obtained:

I ents.

in concentrate sulfuric acid with green coloration. when printed with chromium mordant on cotton it yields a very bright blue oigood fastness to washing and good resistance to disch ing agents.

Exsurn: 13

By reacting 3-sulfobenzylethyl-isorosindulinee-sult'onic acid with 5'-sulfo-4'-hydroxy-3'-carboxy-4-aminodiphenylamine- -z-sulfonic acid at water bath temperature in the presence of'sodium acetate 3 dyestuil' of the following formula is obtained:

H N coon I CHl no N N N/ o k OH O CHI SOIH It dissolves in water with a reddish-blue, in concentrated sulfuric acid with green coloration. When printed with chromium mordant on cotton it yields reddish blue shades of good fastness to washing and good resistance to discharging Exsuru 14 By heating 3-methylcyclohexylisorosinduline- 6.9-disulfonic acid with 5'-sulfo-4'-hydroxy-3- carboxy-4-aminodiphenylamine-2-sulfonic acid in the presence of sodium acetate as dyestuff oi the following formula is obtained:

s cm

coon /N 1 on. no N N N/ N 01H 0|H can" In its dyeing properties it resembles the foregoing dyestuil'.

Exempt: 15

The isorosinduline of vic.-m-xylyl-p-naphthylamine and ,nitrosodiethylaniline is condensed with p-aminosalicylic acid to the corresponding safranine by oxidation with air; the safranine thus obtained is transformed into the disulfonic acid by heating it for some hours with five times its quantity of a 32% oleum at a temperature of about 30 0.:

- coon HOQN N main),

BIC CHI soin' The dyestufl dissolves in concentrated sulfuric l5 acid with green and in water with bluish-violet coloration. Dyed on wool from an acid bath it yields a clear, rich, reddish blue of good fastness properties. By after-treatment with chromium yielding agents the dyeings become bluer ot'otherwise good fastness properties.

With chromium mord'ant printed on cotton bright blue shades of good iastness to washing and good resistance to discharging, agents are obtained.

EXAMPLE 16 By heating 3-diethylisorosinduline-1.6-disulionic acid with 4'-aminogallani1ide in dilute alcohol in the presence of sodium acetate at first an insoluble l-monosulfonic acid of the corre- 0H Hop -i SOaH SOIH

The sodium salt of the dyestuii? dissolves in water with clear greenish-blue, in concentrate sulionic acid with green coloration.

With chromium mordant printed on cotton thedyestuff yields clear greenish blue shades of very good fastness to washing and very good resistance to discharging agents.

EXAMPLE 17 By heating 1-chloro-3-diethylisorosinduline- 6.9-disulfonic acid with 5-sulIo-3-amino-2-hydroxybenzoic acid in the presence of sodium acetate a dyestufi is obtained, which dissolves in water with clear reddish blue and in concentrated sulfuric acid 'with green coloration:

' N HOaB QN N Nrclm), n'oo H With chromium mordant printed on cotton the dyestufl yields clear blue shades of good iastness to washing and good resistance to discharging agents.

EXAMPLE 18 By reacting the corresponding hexahydro-3- diethylisorosinduline-l.fi-disulionic acid with 5'- sulfo 4'- hydroxy-3'- carboxy-e-aminodiphenylamine-Z-sulfonic acid in the presence of sodium acetate whiie heating to 80-90? C. a dyestuff of the following formula is obtained:

coon HOQNQN N was).

01H 7 OaH H\ H2O CH2 The dyestuff obtained dissolves in water with clear blue and in concentrated sulfuric acid with green coloration. With chromium mordant printed on cotton the dyestufi yields clear blue shades of good fastness to washing and good resistance to discharging agents.

EXAMPLE 19 i In analogous manner as described in the foregoing example, a dyestufi. of the formula:

N(C:Hu):' N

COOH

is obtained from the corresponding isorosindulinel.6-disulfonic acid. It dissolves in water with greenish blue, in concentrated sulfuric acid with green' coloration and yields, when printed on cotton with chromium mordant, rich greenish blue shades of good fastness to washing and good resistance to discharging agents.

EXAMPLE 20 Similar in preparation and properties is the dyestufl of the following formula:

COOK

- ExAMPLn 21 In analogous manner as described in the foregoing example by heating the corresponding 1.6- disulfonic acid with 5'-sulfo-4'-hydroxy-,3'-carboxy-4-aminodiphenylamine-2-sulfonic acid in the presence of sodium acetate 2. dyestufl of the following constitution is obtained;

The dyestufl dissolves in water with clear blue,

- in concentrate sulfuric acid with green coloration;

printed on cotton with chromium mordant it yields rich clear blue shades oi very good fastness to washing and very good resistance to discharging agents.

Exams: 22

The dyestufi of the formula:

COOH

is obtained in analogous manner as the foregoing ones. It is of somewhat redder shade than these, but otherwise of the same properties.

We claim:

1. As new products the dyestufls corresponding in the free state to the general formula:

1 [seal wherein R1 and R: stand for a member of the group consisting of hydrogen, allwl, aryl, aralkyl andhydroaryLRastandsioramemberotthe group consisting of hydrogen, hydroxyl, alkyl-- amino-, arylaminoand aroylamino-radicals, X

stands for a member or the group consisting of alkyl, aryl, aralkyl and hydroaryl, Y stands for a member or the group consisting of hydrogen, alkyl, halogen and hydrcxyl, m and 2: stand for whole numbers, n being at least 2, and wherein one o-hydroxycarboxylic acid grouping is attached to one or the group consisting ot x, III, IV, R1, R2 and R: and at least one SOaH-group is attached to one of the group consisting of x, 11, I11 and IV.

/N I v i HOQNQN N menial one on: cm

2. As new products the dyestufis corresponding in the free state to the general formula:

, amino-, arylaminoand aroylamino-radicals, Y

stands for a member or the group consisting of hydrogen, alkyl, halogen and hydroxyl, m and 11 stand for whole numbers, n being at least 2,

and wherein one o-hydroncarboxylic acid grouping is attached to one of the group consisting of "ary III, IV, R1, and R: and R: and at least one SOsH-group is attached to one of the group consisting of aryl," II, III and IV.

8. As new products .the dyestuil's corresponding in the free state to the general formula:

wherein R1 and R: stand for a member of the group consisting of hydrogen, alkyl, aryl, aralkyl and hydroaryl, R: stands for a member or the group consisting of hydrogen, hydroxyi, a'ikylamino-, arylaminoand aroylamino-radicals, Y stands tor a member of the group consisting of hydrogen, alkyl, halogen and hydroxyl, m and 1: stand for whole numbers, n being at least 2, and wherein one o-hydromcarboxylic acid grouping k attached to one of the group consisting of I, III, IV, R1, R: and R: and at least one SOaH-group is attached to one 01. the group consisting of I, II, III and IV.

4. As new product the dyestufl. corresponding inits i'ree state to the formula;

son!

OOH

assess? t 7 5. As new product the dyestuir corresponding inits f-ree stateto the formulli nooc /N a I BOON N N/ mean 10 A 6. as new product the dyestui! corresponding in its free state to the formula:

QN N memo. H0

7. Process for the production oi dyeings according to the chromium printing-process which comprises printing on fibers with a chromium printing paste which curtains as essential in- 5 gredient a dyestufl as claimed in claim 1.

8. Process for the production oi dyeings according to .thechromium printing process which comprises printing on fibers with a chromium printing paste which contains as essential ingredient a dyestufl as claimed in claim 2.

9. Process ior the production of dyeings according to the chromium prin Process which printingonfiberswithachromiumi' gredient a dyes-tuft as claimed in claim 5.

12. Process for the production of dyeings according to the chromium printing process which comprises printing on fibers with a chromium printing paste which contains as essential ingreclient a dyestui! as claimedin claim 6. -13. Fibers dyed with the chrome derivative of a dyestuii, as claimed in claim 1.

14'. Fibers dyed with the chrome derivative 0! 15 a dyestufl. as claimed in claim 2.

15. Fibers dyed with the chrome derivative of a dyestufl, as claimed in claim 3.

16. Fibers dyed with the chrome derivative oi the dyestufl of claim 4.

17. Fibers dyed with the chrome derivative of the dyestui! 0! claim 5.

18. fibers dyedwith the chrome derivative of the dyatui! 0! claim 6.

CARL 36mm.

EUGEN HUBER. 

